CN1890402B - 铝或铝合金用3价铬酸盐液和使用其在铝或铝合金表面形成耐腐蚀性覆膜的方法 - Google Patents
铝或铝合金用3价铬酸盐液和使用其在铝或铝合金表面形成耐腐蚀性覆膜的方法 Download PDFInfo
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Abstract
本发明的目的在于提供一种使用不含有有害的6价铬的3价铬酸盐液在铝或铝合金表面形成耐腐蚀性优异且与涂料的密合性优异的覆膜的方法。本发明提供一种铝或铝合金用3价铬酸盐液,其中,3价铬浓度是0.01~100g/L的范围,选自由锌、钴、镍及其组合所组成的组中的金属的浓度是0.01~100g/L的范围,氟浓度是0.01~50g/L的范围,并且不含6价铬。
Description
技术领域
本发明涉及铝或铝合金用3价铬酸盐液和使用该3价铬酸盐液在铝或铝合金表面形成耐腐蚀性覆膜的方法。
背景技术
铝或铝合金因重量轻且易于加工、易于铸造、光或热、电或真空特性等,在不适合使用钢铁的领域被大量应用。另外,随着技术的进步,胶粘性等也变得容易,在建筑或运输方面不用说,在汽车、电车、飞机、家电制品等各种领域被利用。此外,近年来,由于环境问题、铝的再制(再生)容易等原因,铝或铝合金被循环使用的量也多,需求也有增长的趋势。
其中,以提高耐腐蚀性和与涂料的密合性为目的,对铝和铝合金施加6价铬酸盐处理等的表面处理。然而,上述的6价铬酸盐处理由于作为主要成分使用6价铬,不仅在处理液中含6价铬,在6价铬酸盐覆膜中也含有6价铬。该6价铬已被指出对人体和环境带来恶劣影响,最近,限制6价铬的使用的动向变得活跃起来。
作为其取代技术之一公开了使用3价铬的无6价铬表面处理方法(例如参照专利文献1~4),但不具有6价铬酸盐程度的充分的耐腐蚀性和与涂料的密合性,处于尚未工业化的现状。
专利文献1:日本专利特开平6-173027号公报
专利文献2:日本专利特开平7-126859号公报
专利文献3:日本专利特开平11-152588号公报
专利文献4:日本专利特开平11-335865号公报
发明内容
本发明的目的在于提供一种使用不含有有害6价铬的3价铬酸盐液在铝或铝合金表面形成耐腐蚀性和与涂料的密合性优异的覆膜的方法。
本发明是基于下述见解而进行的,即,在铝或铝合金表面,通过使用含有选自由锌、钴、镍及其组合所组成的组中的金属和氟的3价铬酸盐液形成3价铬酸盐覆膜,可有效地解决上述课题。
因此,本发明提供一种铝或铝合金用3价铬酸盐液,其中,3价铬浓度是0.01~100g/L的范围,选自由锌、钴、镍及其组合所组成的组中的金属的浓度是0.01~100g/L的范围,氟浓度是0.01~50g/L的范围,并且不含6价铬。
另外,本发明提供一种在铝或铝合金的表面形成耐腐蚀性覆膜的方法,该方法包括使铝或铝合金的表面与权利要求1~3中任意1项所述的3价铬酸盐液接触的工序。
根据本发明,可以在铝或铝合金表面形成耐腐蚀性和与涂料的密合性优异的覆膜。由此,不使用以往使用的有害的6价铬,今后广泛地在各种领域中安全地使用。
具体实施方式
作为在本发明中使用的基底,可以列举铝或铝合金的板状物、长方体、圆柱、圆筒、球状物或压铸件、浇铸件等各种形状的物体。
本发明的3价铬酸盐液包含:3价铬,选自由锌、钴、镍及其组合所组成的组中的金属,以及氟。
作为3价铬源,可以使用选自由氯化铬、硫酸铬、硝酸铬、醋酸铬等的3价铬盐以及用还原剂将铬酸或重铬酸盐等的6价铬还原成3价的3价铬所组成的组中的1种或2种或2种以上。3价铬的浓度 优选是水溶液中0.01~100g/L的范围、更优选是0.05~20g/L的范围。当3价铬的浓度在上述范围内时,可以连续地形成稳定的3价铬酸盐覆膜,可得到优异的耐腐蚀性。
作为锌源,可以列举氯化锌、硫酸锌、硝酸锌、醋酸锌、氢氧化锌、氧化锌、碳酸锌等的锌化合物。这些锌化合物可以使用1种或混合2种或2种以上使用。锌的浓度优选是水溶液中0.01~100g/L的范围、更优选是0.05~20g/L的范围。
作为钴源,可以列举氯化钴、硫酸钴、硝酸钴、醋酸钴等的钴化合物。这些钴化合物可以使用1种或混合2种或2种以上使用。钴的浓度优选是水溶液中0.01~100g/L的范围、更优选是0.1~50g/L的范围。
作为镍源,可以列举氯化镍、硫酸镍、硝酸镍、醋酸镍等的镍化合物。这些镍化合物可以使用1种或混合2种或2种以上使用。镍的浓度优选是水溶液中0.01~100g/L的范围、更优选是0.1~50g/L的范围。
将上述金属混合2种或2种以上使用时,金属的总计浓度优选是水溶液中0.01~100g/L的范围、更优选是0.1~50g/L的范围。
作为氟源,可以列举氟化氢、氟化钠、氟化铵、氟化钾、氟化氢钠、氟化氢铵、氟化氢钾、硅氟化物、硼氟化物等的氟化合物。这些氟化合物可以使用1种或混合2种或2种以上使用。氟的浓度优选是水溶液中0.01~50g/L的范围、更优选是0.05~10g/L的范围。
本发明的3价铬酸盐液,优选pH值在0.5~6的范围、更优选在1.0~4.0的范围。另外,为了调节pH,可以使用盐酸、硫酸、硝酸等无机酸或碱金属类氢氧化物、氨水等碱剂。
另外,本发明的3价铬酸盐液,即使不含磷化合物也能够达到充分的耐腐蚀性。相反,在本发明的3价铬酸盐液中若存在磷,就 产生沉淀,因此不选。
本发明中使用的处理液中上述必需成分以外的残余成分是水。
本发明的3价铬酸盐耐腐蚀性覆膜的形成方法,包括使铝或铝合金表面与上述3价铬酸盐液接触的工序。还可以根据需要,在形成耐腐蚀性覆膜之后,进行水洗、干燥等的处理。作为使铝或铝合金表面与上述3价铬酸盐液接触的工序,可以列举例如将铝或铝合金表面浸渍在上述3价铬酸盐液中的工序,在铝或铝合金表面喷上上述3价铬酸盐液的工序等。将铝或铝合金表面浸渍在上述3价铬酸盐液中的工序例如优选于10~80℃的液温浸渍5~600秒钟、更优选于20~60℃的液温浸渍15~120秒钟。另外,优选形成厚度为0.01~2μm的3价铬酸盐覆膜、更优选是0.02~0.5μm。
另外,作为3价铬酸盐覆膜形成的前处理,还可以根据需要对铝或铝合金表面进行脱脂、蚀刻、活化等与以往形成6价铬酸盐覆膜时同样的处理。
进一步,以提高耐腐蚀性、改善外观、着色等为目的,在形成3价铬酸盐覆膜之后,还可以施加包括涂装的外层涂覆等。
实施例
如下所示,对铝或铝合金表面进行脱脂、蚀刻(实施例)和活化之后,形成3价铬酸盐覆膜。另外,在各工序之间进行水洗,形成3价铬酸盐覆膜后干燥。
脱脂使用DIPSOL公司生产的AL-47进行(30mL/L:于50℃浸渍5分钟)。
蚀刻使用DIPSOL公司生产的#91进行(25g/L:于50℃浸渍30秒钟)。
活化使用62%硝酸(500mL/L)或DIPSOL公司生产的ALZ-740(150g/L)+62%硝酸(750mL/L)进行(室温下浸渍20秒钟)。
干燥是在60℃下进行10分钟。
耐腐蚀性评价方法按照JIS Z2371标准,进行35℃、5%盐水喷雾试验,对240小时后的生锈面积以5个等级评价。
密合性评价方法是在形成并干燥3价铬酸盐覆膜之后,放置约24小时,将该试样浸渍在溶剂类涂料中,进行烧结,再放置24小时之后在煮沸的纯水中浸渍小时,取出放置约1小时后,进行横切粘附试验并进行带剥离,以5个等级评价。
(实施例1)
将A1100(铝平板50×70×0.8mm)脱脂、活化后,在含有5g/L硝酸铬、1g/L硫酸锌、1g/L氟化铵的水溶液中于30℃浸渍30秒钟,然后进行水洗和干燥。3价铬酸盐液的pH值是2,3价铬酸盐覆膜的厚度是0.06μm。
(实施例2)
将A2017(铝合金平板50×70×0.8mm)脱脂、活化后,在含有5g/L硝酸铬、1g/L硫酸锌、1g/L氟化铵的水溶液中于30℃浸渍30秒钟,然后进行水洗和干燥。3价铬酸盐液的pH值是2,3价铬酸盐覆膜的厚度是0.13μm。
(实施例3)
将ADC12(铝模铸平板50×70×3mm)脱脂、蚀刻、活化后,在含有5g/L硝酸铬、1g/L硫酸锌、1g/L氟化铵的水溶液中于30℃浸渍30秒钟,然后进行水洗和干燥。3价铬酸盐液的pH值是2。
(实施例4)
将A2017(铝合金平板50×70×0.8mm)脱脂、活化后,在含有5g/L硝酸铬、2g/L硫酸钴、1g/L氟化铵的水溶液中于30℃浸渍30秒钟,然后进行水洗和干燥。3价铬酸盐液的pH值是2。
(实施例5)
将A2017(铝合金平板50×70×0.8mm)脱脂、活化后,在含有5g/L硝酸铬、2g/L硫酸锌、5g/L硫酸钴、1g/L氟化氢铵的水溶液中于30℃浸渍30秒钟,然后进行水洗和干燥。3价铬酸盐液的pH值是2,3价铬酸盐覆膜的厚度是0.15μm。
(对照例1)
将A1100(铝平板50×70×0.8mm)脱脂、活化后,在含有10g/L三氧化铬、1g/L氟化氢铵的水溶液中于25℃浸渍60秒钟,然后进行水洗和干燥。6价铬酸盐液的pH值是1,6价铬酸盐覆膜的厚度是0.06μm。
(对照例2)
将A2017(铝合金平板50×70×0.8mm)脱脂、活化后,在含有10g/L三氧化铬、1g/L氟化氢铵的水溶液中于25℃浸渍120秒钟,然后进行水洗和干燥。6价铬酸盐液的pH值是1,6价铬酸盐覆膜的厚度是0.03μm。
所得到的结果在表1中示出。实施例1~5中3价铬酸盐覆膜具有与对照例1和2中6价铬酸盐覆膜同等程度的耐腐蚀性和密合性。
盐水喷雾试验 密合性
1:锈0% 1:无剥离
2:锈小于5% 2:剥离小于5%
3:锈小于10% 3:剥离小于10%
4:锈小于50% 4:剥离小于50%
5:锈50%以上 5:剥离50%以上
Claims (8)
1.一种用于铝或铝合金的3价铬酸盐液,其中3价铬浓度是0.01~100g/L的范围,选自由锌、钴、镍及其组合所组成的组中的金属的浓度是0.01~100g/L的范围,氟浓度是0.01~50g/L的范围,并且不含6价铬,上述成分以外的残余成分是水。
2.根据权利要求1所述的3价铬酸盐液,其中不含磷。
3.根据权利要求1或2所述的3价铬酸盐液,其pH值在0.5~6的范围。
4.在铝或铝合金表面形成耐腐蚀性覆膜的方法,该方法包括使铝或铝合金的表面与权利要求1~3中任意1项所述的3价铬酸盐液接触的工序。
5.根据权利要求4所述的方法,所述接触工序包括将铝或铝合金的表面在权利要求1~3中任意1项所述的3价铬酸盐液中于10~80℃的温度浸渍5~600秒钟。
6.根据权利要求4所述的方法,所述接触工序包括在铝或铝合金的表面喷上权利要求1~3中任意1项所述的3价铬酸盐液的工序。
7.根据权利要求4~6中任意1项所述的方法,还包括对铝或铝合金的表面进行脱脂和活化的工序。
8.根据权利要求7所述的方法,还包括对铝或铝合金的表面进行蚀刻的工序。
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PCT/JP2004/018258 WO2005056876A1 (ja) | 2003-12-09 | 2004-12-08 | アルミニウム又はアルミニウム合金用3価クロメート液及びそれを用いたアルミニウム又はアルミニウム合金表面に耐食性皮膜を形成する方法 |
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WO2007134152A1 (en) * | 2006-05-10 | 2007-11-22 | Henkel Ag & Co. Kgaa. | Improved trivalent chromium-containing composition for use in corrosion resistant coating on metal surfaces |
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